Process for the preparation of a diazo pigment from a diazoamino compound

ABSTRACT

AN IMPROVED PROCESS FOR THE MANUFACTURE OF A DISAZO PIGMENT OF THE FORMULA R-N=N-CH(-CO-CH3)-CO-HN-A-NH-CO-CH(-CO-CH3)-N=N-R   IN WHICH A REPRESENTS AN ARYLENE RADIACALF AND R REPRESENTS AN ARYL RADICAL, WHEREIN A DIAZOAMINO COMPOUND OF AN ARYLAMINE IS HEATED WITH A BISACETOACETYL-ARYLENEDIAMINE IN AN ORGANIC SOLVENT.

United States Patent PROCESS FOR THE PREPARATION OF A DIAZO PIGMENT FROM A DIAZOAMINO COMPOUND Karl Renee and Willy Mueller, Riehen, Switzerland,

assignor to Ciba-Limited, Basel, Switzerland No Drawing. Filed Sept. 26, 1967, Ser. No. 670,760

Claims priority, appliczlltionms/yfivigzerland, Oct. 5, 1966,

Int. cl.c09b 27/00 US. Cl. 260-176 4 Claims ABSTRACT OF THE DlSCLOSURE German specification No. 1,150,165 describes a process for the manufacture of yellow 'disazo pigments by condensing a dihalide of a dicarboxylic acid of the formula in which A and B represent aryl radicals, with 2 mols of a primary monamine. While this process furnishes products having excellent pigment properties, it has the disadvantage that it must be carried out in an anhydrous organic solvent and that the formation of the dicarboxylic acid halide and the condensation with the monoamine require two separate process steps.

a The present invention is based on the observation that the desired disazo pigments can be obtained in an excellent yield and in a form well suited for pigment purposes by coupling the diazoamino compound of a diazotized arylamine with a bisacetoacetyl compound of the formula in an organic solvent, or if desired'in an aqueous organic solution, preferably in the presence of an acid, whereby the diazoamino, compound is thermally split and coupling takes place instantaneously.

The diaz'oamino, compound used is preferably one of the formula 3,657,219 Patented Apr. 18, 1972 in which V represents a hydrogen or halogen atom, or an alkyl, alkoxy or carbalkoxy group, V a hydrogen or halogen atom, X, Y and Z each a hydrogen or halogen atom, or an alkyl, alkoxy, a possibly substituted phenoxy, nitro, trifluoromethyl, cyano or carbalkoxy group; also amines of the formula in which X and Y each represents a hydrogen or halogen atom or an alkyl or alkoxy group, R 21 hydrogen atom or an alkyl group, and R represents a hydrogen atom or an alkyl or aryl residue.

As examples of the compounds of the Formula 4 the following aminocarboxylic acid arylides may be mentioned:

3-aminobenzoic acid anilide,

4-arninobenzoic acid anilide,

4-chloro-3-arninobenzoic acid anilide,

4-chloro-3-aminobenzoic acid-3'-chloranilide,

4-chloro-3-aminobenzoic acid-2'-methyl-3'- chloranilide,

4-chloro-3-aminobenzoic acid-2-methyl-5- chloranilide,

4-chloro-3-aminobenzoic acid-3-trifluoromethylanilide,

4-chloro-3-aminobenzoic acid-2-chloro-5- trifluoromethylanilide,

4-chloro-3-aminobenzoic acid-3,5'-di-trififluoromethylanilide,

4-chloro-3-aminobenzoic acid-2,4,5'-trichloranilide,

4-chloro-3-aminobenzoic acid-2',4'-dichloranilide,

4-chloro-3-aminobenzoic acid-2',5'-dichloranilide,

2,4-dichloro-3-aminobenzoic acid-3-trifluoromethylanilide,

2,4-dichloro-S-aminobenzoic acid-2',4',5-trichloranilide,

2,4-dichloro-S-aminobenzoic acid-2'chloro-5-trifluoromethylanilide,

4-methoxy-2-chloro-5-aminob'enzoic acid-3'-trifluoromethylanilide,

4-chloro-3-aminobenzoic acid-2'-phenoxy-5-trifluoromethylanilide,

4-chloro-3-aminobenzoic acid-2' (4"-chlorophenoxy) 5-trifiuoromethylanilide,

4-chloro-3-aminobenzoic acid-2'-(2",4",5"-trichlorophenoxy)-5'-trifluoromethylanilide,

4-chloro-3-aminobenzoic acid-2-(4"-methylphenoxy)- 5'-triflu0romethylanilide,

4-chloro-3-aminobenzoic acid-2'-( "-methoxyphenoxy)-' 5-trifiuoromethylanilide.

As examples of compounds of the Formula 5 there may be mentioned:

3-amino-4-chlorobenzene-sulphonic acid anilide,

3-amino-4 chlorobenzenesulphonic acid-2',4'dichloranilide,. v

3-amino-4-methylbenzenesulfonic acid anilide,

3-amino-4-methylbenzenesulphonic acid-3'-trifiuoromethylanilide,

3-amino-4-methoxybenzenesulphonic acid anilide,

3-amino-4-methoxybenzenesulphonic acid-2,5'- dichloranilide, 1

2,S-dimethoxy-4-aminobenzenesulphonic acid anilide, 2,5-dimethoxy-4-aminobenzenesulphonic acid-2'-chloranilide, 2,S-dimethoxy-4-aminobenzenesulphonic acid-2',4'-dichloranilide, 2,5-dimethoxy-4-aminobenzenesulphonic acid-2',5'-

dichloranilide, 2,5-dimethoxy-4-aminobenzenesulphonic acid-2',4',5'-

trichloranilide, 2-methoxy-5-methyl-4-aminobenzenesulphonic acid anilide, 2,5-dimethyl-4-aminobenzenesulphonic acid anilide, 4-methoxy-3-aminobenzenesulphonic acid amide, 4-methoxy-3-aminobenzenesulphonic acid dimethylamide, 4-methoxy-3 -aminobenzenesulphonic acid ethylamide.

The aryldiazoamides to be used in the present process are obtained in the known manner by coupling an aryldiazonium salt with a primary or preferably a secondary amine. For this purpose a wide variety of amines are suitable, for example, aliphatic amines such, for example, as methylamine, ethylamine, ethanolamine, propylamine, isopropylamine, butylamine, hexylamine and especially dimethylamine, diethylamine, methylethanolamine, dipropylamine or dibutylamine, aminoacetic acid, N-methylaminoacetic acid, butylaminoacetic acid, aminoethanesulphonic acid, N-methylaminoethanesulphonic acid, guanylethanesulphonic acid, B-aminoethyl-sulphuric acid; alicyclic amines such, for example, as cyclohexylamine, N- methyl-cyclohexylamine, dicyclohexylamine; aromatic amines such for example, as 4 aminobenzoic acid, sulphanilic acid, 4 sulpho 2 aminobenzoic acid, 4 sulphophenylguanidine, 4 N-methylaminobenzoic acid, 4- N-ethylaminobenzoic acid, 1 amino-naphthalene-4-sulphonic acid, 1 aminonaphthalene-Z,4-disulphonic acid; heterocyclic amines such, for example, as piperidine, morpholine, pyrrolidine, and finally also sodium cyanimed or dicyandiamide. The amines may be further described as wherein R is hydrogen or lower alkyl and R is lower alkyl, hydroxyethyl, carboxymethyl, (sulfonic acid)ethyl, carboxyphenyl, sulfophenyl, sulfo-carboxyphenyl, sulfophenylformamidino, sulfonaphthyl or cyanoformamidino or R and R are each cyclohexyl and R and R together with the nitrogen atoms form a piperidine, morpholine or pyrrolidine ring.

As a rule, the diazoamine compounds obtained are sparingly soluble in cold water and can be isolated from the reaction media in crystalline form by salting out. In many cases the moist press cakes, as they result from the manufacture, may be used directly for the further reaction. In some cases it may prove advantageous to dehydrate the diazoamides by vacuum drying before the reaction or to suspend them in an organic solvent and then to remove the water by azeotropic distillation.

The bisacetoacetyl compounds of the Formula 2 to be used as coupling components contain as the arylene radical preferably one of the formula in which X, and X each represents a hydrogen or halogen atom or an alkyl or alkoxy group, Y, a hydrogen or halogen atom or an alkyl, alkoxy or trifiuoromethyl group, and Y represents a hydrogen or halogen atom.

These compounds are obtained by simply reacting an acetoacetic acid ester or diketene upon an aromatic diamine such, for example, as

1,4-diaminobenzene,

1,3-diaminobenzene, 1,3-diamino-4-methoxybenzene, 1,3-diamino-4-methylbenzene, 1,3-diamino-4-chloorbenzene, 1,4diamino-2-chlorobenzene, 1,4-diamino-2-bromobenzene, l,4-diamino-2,5-dichlorobenzene, 1,4-diamino-2-chloro-S-methylbenzene, 1,4-diamino-2-chloro-S-methoxybenzene, 1,4-diamino-Z-methylbenzene, l,4-diamino-2,S-dimethylbenzene, 1,4-diamino-2-methyl-S-methoxybenzene, 1,4diamino-2-methoxybenzene, l,4-diamino-2,5-dimethoxybenzene, l,4-diamino-2,5-diethoxybenzene, 1,3-diamino-4,6-dimethylbenzene, 1,3-diamino-2,6-dimethylbenzene, 4,4-diaminodiphenyl,

3 ,3'-dichloro-4,4-diaminophenyl,

3,3 '-dimethyl-4,4-diaminodiphenyl, 3,3-dimethoxy-4,4'-diaminodiphenyl,

3,3 ',6,6-tetrachloro-4,4'-diaminodiphenyl, 3,3'-dimethyl-6,6'-dichloro-4,4-diaminodiphenyl, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 1,4-diaminonaphthalene, 2,8-diaminochrysene,

4,1 l-diaminofluoranthene.

The coupling of the diazoamino compound with the bisacetoacetylamino compound is carried out in an organic solvent, for example in chlorobenzene, o-dichlorobenzene, nitrobenzene, pyridine, quinoline, ethyleneglycol, ethyleneglycol monomethyl or monoethyl ether, dimethylformamide, N-methylpyrrolidone, formic acid or preferably in acetic acid. I k

tln general, it is not necessary to use the diazoamino compound in the anhydrous form. It is possible to use, for example, the suction filter cake still moist with water. The splitting of the diazoamino compound preceding the coupling is preferably carried out in an acidic medium. When a neutral solvent is used, an acid, for example hydrochloric, sulphuric, formic or acetic acid, must be added.

The coupling reaction is advantageously conducted at an elevated temperature, preferably between 60 and C. and in general it proceeds rapidly and quantitatively.

By virtue of their insolubility the resulting pigments can be filtered off from the reaction mixture. Since the by-products remain dissolved, the resulting pigments are obtained in an excellent purity so that in most cases an after-treatment with an organic solvent, as is needed with pigments obtained by the aqueous coupling process, can be dispensed with. It is another advantage of the process of this invention that the yield is high, and the pigments are obtained in a form very suitable for pigment uses and the tinctorial properties are constant.

The pigments obtained by the present process may be used for a wide variety of pigment applications because of their favourable properties, for example in a finely dispersed form for dyeing rayon'and viscose or cellulose ethers or esters or superpolyamides or superpolyurethanes or polyesters in the spinning mass, and also for the manufacture of coloured lacquers and lakes, solutions or products from acetylcellulose, nitrocellulose, natural resins or synthetic resins such as polymerisation resins or condensation resins, for example aminoplasts, alkyd resins,

phenoplasts, polyolefine's such, for example, as polystyhot glacial acetic acid, methanol and water, to yield 81 rene, polyvinylchloride, polyethylene, polypropylene, polyparts (=85.6% of theory) of the dyestuff of the formula acrylonitrile, rubbencasein, silicone and silicone resins. F a up Furthermore, they may be used advantageously in the 3 t 5 manufacture of colour pencils, cosmetics or laminated 5 1110 or 3 0.0mm panels.

The following examples illustrate the invention. Unless otherwise indicated, parts and percentages are by weight. 'l 'f EXAMPLE 1 f 82 parts of the diazoamino compound of the formula 3 3 r a. in the form of a yellow pigment which is sparingly soluble 3 to insoluble in the conventional solvents and produces b-izce q g on polyvinylchloride yellow tints of excellent fastness to o migration, overlacquering and light.

The following table lists a number of further pigments n n n -ea -co'ox obtained by coupllng the d1azoam1no compounds formed [obtained by coupling diazotized 4-methoXy-3-aminobenfrom the diazo compounds of the aminobenzenes in zoic acid-(3'-trifluoromethyl) anilide with sarcosine in Column I and the stabilizers shown in Column II with an alkaline medium] and 30.5 parts of 2,5-bisacetoacetylthe bisacetoaceyl compounds of the diamines listed in amino-1, 4-dimethylbenzene are stirred in 1600 parts of Column III as described in this example. Column IV glacial acetic acid for 90 minutes at 110 to 115 C. The shows the colour of a polyvinylchloride foil manufactured deep yellow pigment is filtered off hot and washed with with the pigment concerned.

No. I II 111 IV 1 4-chl 1)r)-3-aminobenzoic aeid-2,5-diehloro- Methyltaurine 2,5-diehloro-l,4-phenylenediamine Greenish yellow.

am 1 e. do Diethylamine. 2-ehloro-1,4-phenylenediamine Do. 4chloro-3-aminobenzoie aeid-3-ehloro-2- Methyltaurine LQ-phenylenediamine Do.

moth, lanilide. 4 .do do 2,5-dichloro'1,4-phenylenediamine Do. 610.. (lo 2-ehloro-5methyl-l.4-phenylenediamine. Yellow. (10.. .do 2-chloro-5-methoxy4,4-pl1enyleuediamine Reddish yellow. .do Piperidine 2,fi-dimethyl-l,4-phenylenediamine Do. 4-chloro-3-aminobenzoic acid-5-chloro-2- Morpholine. 2 ehloro-5-methyLLiphenylenediamine Greenish yellow,

methylanilide. 9 do do 2chloro5-methoxy-1,4-phenylenediamine Do.

do (lo. 2,fi-climethoxy-lA-phenylenediamine Reddlsh yellow. 4-chloro-3-aminobenzoic aeid-3-trilluoro- (lo 2,5-dichloro-1,4-phenylenediamine.. Greenish yellow.

methylanilide. l2 do do 2-ehloro-methyl-l,4phenylenediamlue Do. 13-.. 4-ehloro-3-aminobenzoie aeid-2-chloro-5- Diethylamine ..do Do.

trifluoromethylanilide. l4 do do do Yellow. 15 .do .do 2,5-diethoxy-1,4-pheny1enediam Yelloworange. 16" "do" .do 2.4-dimethyl-l,fi-phenylenediamine Yellow. 17.. do .do 3,3-dimethyl-4,4diaminodiphenyl Do. 18 .510 Methyltaurine 4,6 diohloro-l,3-phenylenerliamine Do. 19 ;B-amiEiio-HarbOmethoXybenzoie acid do 2-ch!oro-fi-methyl-l,l-phenylenedia Greenish yellow. do Sarcoxine 2-methyl-5-methoxy-l 4-phenylenediamlne Reddish yellow. 21 2,5-dimwthoxy-4-aminobenzenesulphonie Morpholine .d Do.

acid anilide.

2,5'dlchloro-l,4-phenylenediamine Greenish yellow. ,3-dimethyl-4,4-diaminodiphenyl Yellow.

,5-dieliloro-1,4-phenylenediamine Dn. acid 'diethyl amide. 25 l-amino-Q,4-dimethoxybenzene-fi-sulphonle clo ..d0 Greenish yellow.

acid anilide.

26 4-metliyl-3-aminobenzoie aeid-2-ehlo1'o-5- Dimethylamine do Do. 1 tritluoromethylanilide.

2-methyl-5-chloro-1,4-phenylenediamine. Yellow. 2-methoxy-5-ehloro-1,4phenylenedlamine Do.

2,5-dimethyl 1,4phenylenediamine Reddish yellow. 2-chl0ro-1,4 phenylenediamine" Greenish yellow.

do-. 1,4-phenylenediamlne... Do. do- 2,5-diehloro-1,4-phenylenediamine. Do. do 2-chloro-5-methyl-1,4-phenylenediamine. D 0. .do. 2-chloro-5-methoxy-1,4-phenylenediamine. Do. -do 2,5-dimethyl-1,4-phenylenediamine. Yellow. eh minob enzoio acid hlo sarcosine 1,4-pl1enylenediamine Greenish yellow. phenoxy) -5-trifiuo1'om'ethylanilide. do do 2-chloro-1,4-phenylenediamlne. Do.

-do 2,5diehloro-l,4-phenylenedia1nine; Do. 2-ehloro-5-methoxy-1,4-phenylenediamine. Yellow.

2-ehloro-5-methyl-1,4-phenylenediamlne- Do aminobenzoieaei 1- do lo Greenish yellow. ehlorophenoxy) -6-trifluoromethylanilide.

42 do do 2-ehloro-5-methoxy-l,4-phenylened1am1ne. Yellow.

44 4-ehloro-3-aminobenzole acid2eh1oro-5- Piperidine 2,5-diamino-1-chlorobenzene Yellow.

trifiuoromethylanillde. v v I 45 do 'Aminoacetic acid 2,5-d1amino-1,4-phenylenediamine Greenlsh yellow.

46 do Sulphanilie acid 2,5-diaminobenzene Do.

4 7 2,5-dimethoxy-4-aminobenzenesulphonie Sareosine 2,5-diamino-l-chloroA-mcthylbenzene Do. acid-4-ehloranilide.

4Q. 4-chloro'3-iminohenzoic aeid-2-methyl-5- .do 2,5-d1amino-1,4-dlmethylbenzene Do.

ehloranilide. 1 I

49 4-ehloro-3-aminobenzoic aeid-2-p-ehloro- Piperidme Do.

phenoxy-fi-trifiuoromethylanilide.

50. 4-nitraniline p-Toluenesnlpho-N-ethylamide- 2,5-dichloro-1,4-phenylenediamine Reddish yell w,

51 2-nitro-4-ehloraniline. do do Do.

52. 2ehloro-5-methoxyanilme ...do Yellow.

53. 2,5-(limethoxy-fi-cliloraniline .do do Do.

No. I II III IV 54 4-methoxy-3-aminobenzenesulphonamide Diethylamine 2-chl0ro'5-methoxy-1,4phenylenediamine Greenish yellow, 55 4-methoxy-3-aminobenzenesulpl1one ..do do Do.

diethylamide. 56.-., 4-methox -S-aminobenzenesulphono ..do ..d

morpholide. 57--.. 4 methoxy-3-aminobenzenesulphone do cyclohexylamide. 53 4-methoxyQ-aminobenzenesulphnnilido .do 59 4-methoxy-3-aminobenzenesulpho4- do ..d0

chlornnilide. 60 4-methoxy-3-aminobenzenesulpho-2-el1lorodo .do D

6-trifiuoromethylanilide. 61. 4ehloro-3-amino benzoic acid amide Morpholine do Greenish yellow o2 4-eh1 cir3-3-aminobenz0ie aeid-N-methyl- .do do V D anti 0. 63...- 4Cl1lIlS:10-3-am1HObBDZ0lC aeid-N-diethyldo do a e. 64 4-ehloro-3-amlnobenzoic acid morpholide do 65. 4-mcthyl-3-amlnobenzoic acid amine do. 66 4methoxy-3-aminobenzoic acid amide do. 67 4-carbomethoxy-3-amlnobenz0i0 acid amide do .d0 Greenish yellow, 68- 3-aminobenzoic acid amide d0 do D EXAMPLE 2 2O R4 65 parts of stabilized polyvinylchloride, 35 parts of dioctylphthalate and 0.2 part of the dyestuff obtained III I paragraph ,1 of Example 1 are stirred together and then 5 rolled to and fro for 7 minutes at 140 C. on a two-roll Yl X1 calender. The resulting yellow foil displays very good fastness to light and migration. 025

We claim: 1. A process for the manufacture of a disazo pigment R3 of the formula wherein R is hydrogen or lower alkyl and R is lower alkyl, hydroxyethyl, carboxymethyl, (sulfonic acid)ethyl,

CH; O (JOCH in which A represents a radical of the formula carboxyphenyl, sulfophenyl, sulfo-carboxyphenyl, sulfophenylformamidino, sulfonaphthyl or cyanoformamidino or R and R are each cyclohexyl and R and R together with the nitrogen atom form a piperidine, morpholine or pyrrolidine ring is heated with a compound of the formula Y1 o CH3 OH: i hi h X and X each represents hydrogen, hl i at a temperature of between 60l80 in an inert organic lower alkyl or lower alkoxy, Y represents hydrogen, chlosolvent rine, lower alkyl, lower alkoxy or trifluoromethyl and Y A Process accordlng to clalm 1 Where"! 4 and R5 represents hydrogen or chlorine and R represents a radieach represents lower alkyl and 4 and 5 together Wlth cal of the formula rol1d1ne ring.

the nitrogen atom forms a piperidine, morpholine or pyr- 4. A process as claimed in claim 1, wherein acetic acid is used as organic solvent.

Y X 3. A process as claimed in claim 1, wherein the reac- NHOC or tion is carried out in the presence of an acid selected 1 1 from the group consisting of hydrochloric, sulfuric, formic R1 or ac ti Z V: e c acld in which V represents hydrogen, chlorine, lower alkyl, ces Cited lower alkoxy or lower carbalkoxy, V represents hydro- UNITED STATES PATENTS gen or chlorine and X, Y and Z each stands for hydrogen5 2 793 206 5/1957 Scalera et a1 260203 chlorine, lower alkyl, lower alkoxy or phenoxy, whic may be substituted by chlorine, lower alkyl, lower alkoxy, 3413279 11/1968 Mueller 260 176 nitro, trifluoromethyl, cyano or lower carbalkoxy, X and FOREIGN PATENTS 7 Y each represents hydrogen, chlorine, lower alkyl or T5 3/1966 Germany 260 lower alkoxy, R represents hydrogen or lower alkyl group and R represents hydrogen, lower alkyl or phenyl OTHER REFERENCES I or R and R together with the nitrogen atom may also Houben-Weyl, Methoden der Organischen Chemie, form a morpholine ring; wherein a diazoamino compound 1965, Teil 3, pp. 276-278. of the formula 5 R4 JOSEPH REBOLD, Primary Examiner D. M. PAPUGA, Assistant Examiner Y X V1 5 NHOC In 7 US. Cl. X.R.

Z V2 260416, 140, 152, 156, 397.7, 558 A UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,657,219 Dated April 1 .8, 1972 lnven fl Karl i'ionco et a1.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Colman 1 line 6 delete "Silva-Limited" and substitute CIBA-GEIGY AG Signed and sealed this 7th day of May 197g.

(SEAL) Attest:

EDWARD 1 1 FLETCHER ,JR. 0. MARSHALL DANN Atte sting Officer Commissioner of Patents FORM PC4050 (169) uscoMM-oc 60376-P69 [1.5. GOVERNMENT PRINTING OFFICE 2 19.9 36-33,

. CASE 6026/E @7 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,657,219 Dated April 18, 1972 Inventor(s) KARL RONCO ET AL in the aboveidentified patent It is certified that error appears corrected as shown below:

and that said Letters Patent are hereby Column 8, lines 20-28, claim 1, the structural formula should be amended to read: R

N=N-N N-O S R Signed and sealed this 15th day of May 1973.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents L. l

,jac 

